Abstract

Hematite (α-Fe2O3) is an important candidate electrode for energy system technologies such as photoelectrochemical water splitting. Conversion efficiency issues with this material are presently being addressed through nanostructuring, doping, and surface modification. However, key electrochemical properties of hematite/electrolyte interfaces remain poorly understood at a fundamental level, in particular those of crystallographically well-defined hematite faces likely present as interfacial components at the grain scale. We report a combined measurement and theory study that isolates and evaluates the equilibrium surface potentials of three nearly defect-free single crystal faces of hematite, titrated from pH 3 to 11.25. We link measured surface potentials with atomic-scale surface topology, namely the ratio and distributions of surface protonation–deprotonation site types expected from the bulk structure. The data reveal face-specific points of zero potential (PZP) relatable to points of zero net charge (PZC) that lie within a small pH window (8.35–8.85). Over the entire pH range the surface potentials show strong non-Nernstian charging at pH extremes separated by a wide central plateau in agreement with surface complexation modeling predictions, but with important face-specific distinctions. We introduce a new surface complexation model based on fitting the entire data set that depends primarily only on the proton affinities of two site types and the two associated electrical double layer capacitances. The data and model show that magnitudes of surface potential biases at the pH extremes are on the order of 100 mV, similar to the activation energy for electron hopping mobility. An energy band diagram for hematite crystallites with specific face expression and pH effects is proposed that could provide a baseline for understanding water splitting performance enhancement effects from nanostructuring, and guide morphology targets and pH for systematic improvements in efficiency.

Authors contributing to RSC publications (journal articles, books or book chapters)
do not need to formally request permission to reproduce material contained in this
article provided that the correct acknowledgement is given with the reproduced material.

Reproduced material should be attributed as follows:

For reproduction of material from NJC:
Reproduced from Ref. XX with permission from the Centre National de la Recherche
Scientifique (CNRS) and The Royal Society of Chemistry.

For reproduction of material from PCCP:
Reproduced from Ref. XX with permission from the PCCP Owner Societies.

For reproduction of material from PPS:
Reproduced from Ref. XX with permission from the European Society for Photobiology,
the European Photochemistry Association, and The Royal Society of Chemistry.

For reproduction of material from all other RSC journals and books:
Reproduced from Ref. XX with permission from The Royal Society of Chemistry.

If the material has been adapted instead of reproduced from the original RSC publication
"Reproduced from" can be substituted with "Adapted from".

In all cases the Ref. XX is the XXth reference in the list of references.

If you are the author of this article you do not need to formally request permission
to reproduce figures, diagrams etc. contained in this article in third party publications
or in a thesis or dissertation provided that the correct acknowledgement is given
with the reproduced material.

Reproduced material should be attributed as follows:

For reproduction of material from NJC:
[Original citation] - Reproduced by permission of The Royal Society of Chemistry (RSC) on behalf of the
Centre National de la Recherche Scientifique (CNRS) and the RSC

For reproduction of material from PCCP:
[Original citation] - Reproduced by permission of the PCCP Owner Societies

For reproduction of material from PPS:
[Original citation] - Reproduced by permission of The Royal Society of Chemistry (RSC) on behalf of the
European Society for Photobiology, the European Photochemistry Association, and
RSC

For reproduction of material from all other RSC journals:
[Original citation] - Reproduced by permission of The Royal Society of Chemistry

If you are the author of this article you still need to obtain permission to reproduce
the whole article in a third party publication with the exception of reproduction
of the whole article in a thesis or dissertation.

Information about reproducing material from RSC articles with different licences
is available on our Permission Requests page.